Activated inorganic metal oxides

ABSTRACT

A catalyst system for heterogeneous catalysis of organic compound conversion reactions is disclosed. The system includes a reaction product of (i) a BF3/alcohol catalyst complex and (ii) an activated metal oxide support for the catalyst complex. The reaction product includes an amount of the catalyst complex effective for catalyzing the conversion reaction.

CROSS REFERENCE TO RELATED APPLICATION

This application is based on and claims priority under 35 U.S.C. §119(e)from presently pending U.S. provisional application Ser. No. 61/312,869,filed Mar. 11, 2010, the entirety of the disclosure of which is herebyincorporated by reference.

FIELD OF THE INVENTION

The invention of the present application relates to catalysts used inorganic compound conversion reactions. More particularly, the inventionrelates to an activated metal oxide catalyst used in organic compoundconversion reactions.

BACKGROUND OF THE INVENTION

A great number of different types of catalyst systems have been proposedin the past for conducting organic compound conversion reactions. Thesesystems include the use of such things as (1) Metal Oxide BF₃ Complexes,(2) BF₃ and Liquid BF₃ Complexes as Catalysts for IsobutylenePolymerization, (3) Liquid BF₃ Methanol Complexes as IsobutylenePolymerization Catalysts, and (4) Solid Isobutylene PolymerizationCatalysts. Prior art relevant to these prior art systems is discussedbelow.

Metal Oxide BF₃ Complexes

Inorganic metal oxides, such as alumina, have been provided withcatalytic activity in the past by contacting the same with BF₃, usuallyin gaseous form. The contacting is usually followed by hydrolysis andcalcination or some other post-treatment. These catalysts generally havelimited activity, are not stable and release free BF₃ into the reactionproducts requiring post reaction removal of these residues.

U.S. Pat. No. 2,804,411, assigned to American Oil Company, disclosestreatment of a Si stabilized gelled alumina with gaseous BF₃. Free BF₃is required to be added to the reaction mixture.

U.S. Pat. No. 2,976,338, assigned to Esso, describes an olefinpolymerization catalyst comprising a BF₃₋H₃PO₄ complex that may beabsorbed onto a solid support.

U.S. Pat. No. 3,114,785, assigned to UOP, describes an olefinisomerization catalyst made by contacting anhydrous gamma or thetaalumina with gaseous BF₃ at temperatures from about 100° C. to 150 ° C.for 10 hours or until alumina is saturated. The process of olefinisomerization using the BF₃-alumina catalyst is claimed; the compositionof the catalyst is not claimed.

U.S. Pat. No. 4,407,731, assigned to UOP, claims catalytic compositionsof matter prepared by pre-treating a metal oxide, such as alumina, withaqueous acid and base followed by calcination. The treated gamma aluminais then treated with BF₃ gas at temperatures of 308-348° C. at elevatedpressure to obtain the final catalyst useful for oligomerization andalkylation reactions.

U.S. Pat. No. 4,427,791, assigned to Mobil Oil Co., discloses a methodfor enhancing the activity of metal oxides, such as alumina, by treatingthe alumina with NH₄F or BF₃, contacting this fluoride containingproduct with an ammonium exchange solution and then calcinating thefinal product.

U.S. Pat. No. 4,918,255, assigned to Mobil Oil Co., describes anisoparaffin alkylation catalyst based on metal oxides andaluminosilicate zeolites treated with a Lewis acid, including BF₃, inthe presence of a controlled amount of water or water-producingmaterial. Excess BF₃, to that needed to saturate the metal oxide, isused requiring post reaction BF₃ removal.

U.S. Pat. No. 4,935,577, assigned to Mobil Oil Co., describes acatalytic distillation process using a non-zeolite metal oxide activatedwith BF₃ gas. Excess BF₃, above that needed to saturate the metal oxideis used requiring post reaction BF₃ removal.

BF₃ and Liquid BF ₃ Complexes as Catalysts for IsobutylenePolymerization

The homogenous catalytic polymerization of olefins using gaseous BF₃ andliquid BF3 complexes is well known. The polymers generally so producedare of the highly reactive type wherein a large percentage of thepolymer contains terminal double bonds or has a high vinylidene content.All of these processes require post-reaction removal of the BF₃catalyst.

U.S. Pat. No. 4,152,499, issued to Boerzel et al., describes thesynthesis of polyisobutylene having a degree of polymerization of 10-100units using a blanket of BF₃ gas as the catalyst. The polyisobutyleneproduct was then reacted with maleic anhydride in yields of 60-90%indicating a large portion of vinylidene end groups.

U.S. Pat. No. 4,605,808, issued to Samson, describes production of apolyisobutylene having at least 70% unsaturation in the terminalposition. An alcohol complex of BF₃ was used as the catalyst. Complexingthe BF₃ seems to give better control of the reaction and highervinylidene content.

U.S. Pat. No. 7,411,104, assigned to Daelim Industrial Co., describes amethod for producing highly reactive polyisobutylene from a raffinate-1stream using a liquid BF₃ secondary alkyl ether-tertiary alcoholcomplex. The process requires low reaction temperatures and the catalystcomplex is not stable and must be made in situ. The catalyst must beremoved from the reactor effluent by a post reaction treatment process.

U.S. Pat. No. 5,191,044, issued to Rath et al., discloses a process forpreparing polyisobutylene in which the BF₃ catalyst is completelycomplexed with an alcohol such that there is no free BF₃ in the reactoror in the reaction zones. An excess of alcohol complexing agent isrequired to assure that no free BF₃ is present. The reaction times areon the order of 10 minutes with reaction temperatures of below 0° C.

Rath, in U.S. Pat. No. 5,408,018 describes a multistage process forpreparing highly reactive polyisobutene with a content of terminalvinylidene groups of more than 80 mol % and an average molecular weightof 500-5000 Dalton by the cationic polymerization of isobutene orisobutene -containing hydrocarbon feeds in liquid phase with the aid ofboron trifluoride as catalyst and at from 0° C. to −60° C. comprisespolymerizing in the presence of secondary alcohols with 3-20 carbonatoms and/or ethers with 2-20 carbon atoms.

Olefin polymerization, especially isobutylene polymerization, is anexothermic process. Control of reaction temperature is critical toproduct quality, catalyst life, degree of polymerization and obtainingthe desired pre-selected properties. In the patents cited above, thereaction temperature was controlled by dilute olefin monomerconcentration, complexed catalyst, multi-stage reactions and/or longreaction times and low reaction temperatures. Low reaction temperaturesincrease energy requirements; long reaction times or dilute feed streamsincrease equipment size and equipment cost (capital expenditures).

Liquid BF₃ Methanol Complexes as Isobutylene Polymerization Catalysts

U.S. Pat. Nos. 6,525149, 6,562,913, 6,683,138, 6,884,858 and 6,992,152,to Baxter, et al. al, describe an olefin polymerization process in whichthe polymerization is carried out in the tube side of a heat exchangerunder turbulent flow conditions. The reactor design allows for veryeffective and efficient removal of the heat of reaction such thatrelatively high feed rates and concentrated feed streams may be used.BF₃-methanol complex is used as the catalyst and because this complex isparticularly stable, higher reaction temperatures may be used. TheBF₃-methanol catalyst complex may be preformed, formed in-situ byseparate injection of the methanol complexing agent, or a combination ofboth.

The BF₃ methanol complexes are very stable allowing for higherisobutylene polymerization temperatures not possible with other BF₃oxygenate complexes, particularly higher alcohols, secondary alcohols,ethers and the like. Also, because higher reaction temperatures may beused, reaction rates are increased.

However, in all of the patents cited above, the BF₃, or at leastportions of the BF₃, catalyst are soluble in the polymer products.Residual BF₃ is detrimental to product quality and must be removed asquickly as possible. Hence, these processes must employ some kind ofcatalyst quench and catalyst removal steps subsequent to the reaction.The quenched BF₃ streams cannot be recycled and the BF₃ is lost.

Solid Isobutylene Polymerization Catalysts

Isobutylene and butylene polymerizations have also been conducted usingsolid catalysts, particularly Friedel-Crafts type catalysts such asAlCl₃. The advantage to these processes is that the catalyst is a solidand is not soluble in the product. Catalyst removal and productpurification is much easier than in the BF₃ catalyzed reactions

U.S. Pat. No. 2,484,384, assigned to California Research Corporation,U.S. Pat. No. 2,677,002, assigned to Standard Oil Co., U.S. Pat. No.2,957,930, assigned to Cosden Petroleum Corporation and U.S. Pat. No.3,119,884, assigned to Cosden Petroleum Corporation, all describe AlCl₃catalyzed butylene polymerization processes using a fluidized bedreactor system.

U.S. Pat. No. 4,306,105, assigned to Cosden Petroleum Corporation,describes a chlorinated alumina catalyst prepared by reacting purealumina with pure chlorine. A fluidized bed reactor is utilized forbutene polymerization.

Solid catalysts have also been used to produce olefin polymers with ahigh proportion of terminal vinylidene groups.

U.S. Pat. No. 5,710,225, assigned to Lubrizol, claims the use ofphosphotungstic acid salt to polymerize C₂-C₃₀ olefins to producepolymers with molecular weights in the range of 300-20,000. The use ofphosphotungstic catalyst, in a fixed bed reactor, is also described, butthe flow rate is low and is generally operated as a plug flow reactor.The resulting polymer has an undesirable very high polydispersity. Thefixed bed reactor as described in the example would not be economicallyfeasible.

U.S. Pat. No. 5,770,539, assigned to Exxon Chemical Patents, Inc.,discloses heterogeneous Lewis acids polymerization catalysts, such asBF₃, immobilized in porous polymer substrates. The BF₃ is complexed withthe aromatic rings of cross-linked polystyrene copolymers.

U.S. Pat. No. 5,874,380, assigned to Exxon Chemical Patents, Inc.,claims a solid state insoluble salt catalyst system for thecarbocationic polymerization of olefin monomer in the presence of polaror non-polar reaction medium which comprises at least one salt of astrong acid and a carbocationically active transition metal catalystselected from Groups IIIA, IVA, VA, and VIA of the Periodic Table of theElements.

U.S. Pat. No. No. 6,384,154, assigned to BASF Aktiengesellshaft,discloses a process for preparing halogen free, reactive polyisobutyleneby cationic polymerization over an acidic, halogen free heterogeneouscatalyst comprising oxides and elements from transition or main group I,II, III, IV, V, VI, VII or VIII of the Periodic Table of the Elements.The polymerization is carried out in a fixed bed reactor.

The solid, heterogeneous butylene polymerization catalysts cited abovedo solve the problem of catalyst residues in the reactor effluent,thereby eliminating the need for post reaction treatment. However,conversions are low, space velocities are low and reaction temperaturesare low.

BF₃ activated metal oxides are not described in the prior art aspolymerization catalysts for the manufacture of polybutene orpolyisobutylene. In fact, U.S. Pat. No. 6,710,140 assigned to BASFAktiengesellshaft, claims the use of alumina as a solid deactivator toabsorb BF₃ catalyst residues from polyisobutylene reactor effluents. Theresulting BF₃-alumina complex is described to be not catalytic.

SUMMARY OF THE INVENTION

In accordance with the concepts and principles of the invention of thepresent application, a process is provided for preparing an improvedcatalyst system which may be used in connection with acid catalyzedorganic compound conversion reactions. This catalyst system desirablycomprises a BF₃/alcohol-metal oxide reaction product having increasedactivity over catalyst compositions obtained using other processes andmethods. The

BF₃/alcohol-metal oxide reaction products of the invention are stable atoperating conditions and the organic conversion products made usingthese catalyst systems do not contain catalyst residues and are freefrom boron and fluorine residues. Because the conversion products do notcontain catalyst residues, post reaction catalyst removal is notrequired. Thus, heterogeneous production processes are greatlysimplified through the use of the catalyst systems of the invention ofthe present application.

The catalyst systems of the invention are particularly applicable to theheterogeneous catalytic polymerization of isobutylene in isobutylenecontaining streams to thereby produce polyisobutylenes, and even moreparticularly, highly reactive polyisobutylenes (HR PIB).

The catalyst systems of the invention are particularly well suited foruse in connection with the conduct of acid catalyzed reactions such asdimerization and oligomerization of olefins.

In accordance with the concepts and principles of the invention, ahighly stable catalyst system is provided for heterogeneous catalysis oforganic compound conversion reactions. The system may desirably includea reaction product of (i) a BF₃/alcohol catalyst complex and (ii) anactivated metal oxide support for the catalyst complex. The reactionproduct, which may be referred to as a BF₃/alcohol-metal oxide system,includes an amount of the catalyst complex effective for catalyzingconversion reactions. In particular, the catalyst system of theinvention is useful in connection with conversion reactions such asFriedel-Crafts alkylation, phenolic alkylation, olefin dimerization,olefin oligomerization, olefin polymerization, propyleneoligomerization, propylene polymerization, butylene dimerization,butylene oligomerization, isobutylene dimerization, isobutyleneoligomerization, butylene polymerization, isobutylene polymerization orisoparaffin alkylation. The catalyst systems of the invention are highlystable and are generally not consumed during the reaction. That is tosay, the catalyst systems of the invention do not require regeneration.Moreover, when the catalyst systems of the invention are used in theform of a fixed bed, there is generally no need for treatment of theproduct for removal of catalyst residues.

Preferably, the alcohol of the catalyst system has no alpha hydrogen.Even more preferably the alcohol may comprise a C₁-C₁₀ monohydricalcohol, glycol or polyhydric alcohol. Ideally the alcohol may bemethanol.

Preferably the concentration of the catalyst complex on the alumina mayrange from about 10 to about 30% by weight. Ideally the concentration ofthe catalyst complex on the alumina may range from about 25 to about 30%by weight.

In a preferred embodiment of the invention, the catalyst system may beused in the form of a fixed bed, the activated metal oxide support maycomprise gamma alumina, and the conversion reaction may comprisepolymerization of isobutylene to form a polyisobutylene product.

Desirably the ratio of alcohol to BF₃ in the catalyst complex may rangefrom about 0.5 mole of alcohol per mole of BF₃ to about 2 moles ofalcohol per mole of BF₃. Ideally the ratio of alcohol to BF₃ in thecatalyst complex may range from about 1 mole of alcohol per mole of BF₃to about 1.3 moles of alcohol per mole of BF₃.

In a highly preferred embodiment of the invention, a catalyst system isprovided for the heterogeneous catalysis of an isobutylenepolymerization reaction and the system comprises a reaction product of(i) a BF₃/methanol catalyst complex and (ii) a gamma alumina support forsaid catalyst complex In this highly preferred form of the invention,the ratio of alcohol to BF₃ in the catalyst complex may range from about0.5 mole of alcohol per mole of BF₃ to about 2 moles of alcohol per moleof BF₃, and the concentration of the catalyst complex on the alumina mayrange from about 10 to about 30% by weight. Moreover, the catalystsystem is ideally used in the form of a fixed bed.

In accordance with the another aspect of the invention, a method isprovided for preparing a catalyst system for heterogeneous catalysis ofan organic compound conversion reaction. This method comprises reacting(i) a BF₃/alcohol catalyst complex and (ii) an activated metal oxidesupport for said catalyst complex. The reaction product includes anamount of the catalyst complex effective for catalyzing conversionreactions.

Desirably the alcohol has no alpha hydrogen. Even more desirably, thealcohol may be methanol.

Preferably the concentration of the catalyst complex on the alumina mayrange from about 10 to about 30% by weight.

In a preferred form of the invention, the conversion reaction maycomprise the polymerization of isobutylene to form a polyisobutyleneproduct, the activated metal oxide support may comprise gamma alumina,and the ratio of alcohol to BF₃ in the catalyst complex may range fromabout 0.5 mole of alcohol per mole of BF₃ to about 2 moles of alcoholper mole of BF₃.

In a highly preferred form of the invention, a method is provided forpreparing a catalyst system for heterogeneous catalysis of anisobutylene polymerization reaction. In accordance with this highlypreferred form of the invention, the method comprises reacting (i) aBF₃/methanol catalyst complex and (ii) a gamma alumina support for saidcatalyst complex. Ideally the ratio of alcohol to BF₃ in the catalystcomplex may range from about 0.5 mole of alcohol per mole of BF₃ toabout 2 moles of alcohol per mole of BF₃, and the concentration of thecatalyst complex on the alumina may range from about 10 to about 30% byweight.

The invention also provides a method for conducting an organic compoundconversion reaction wherein a selected reactive organic compound iscontacted with a catalyst system as set above. In particular, theinvention provides a method for conducting an isobutylene polymerizationreaction which comprises contacting isobutylene with a catalyst systemthat comprises a reaction product of (i) a BF₃/methanol catalyst complexand (ii) a gamma alumina support for said catalyst complex In thishighly preferred form of the invention, the ratio of alcohol to BF₃ inthe catalyst complex may range from about 0.5 mole of alcohol per moleof BF₃ to about 2 moles of alcohol per mole of BF₃, and theconcentration of the catalyst complex on the alumina may range fromabout 10 to about 30% by weight. Moreover, the catalyst system isideally used in the form of a fixed bed.

DETAILED DESCRIPTION OF THE INVENTION

The object of the invention is to provide an activated metal oxidecatalyst composition or system that may be used in a wide range oforganic compound conversion reactions requiring an acid catalyst.Organic conversion reactions may include, but are not limited to,Friedel-Crafts alkylation, phenolic alkylation, olefin dimerization andoligomerization, olefin polymerization, propylene oligomerization andpolymerization, butylenes and isobutylene dimerization andoligomerization, butylenes and isobutylene polymerization, isoparaffinalkylation and the like.

A preferred embodiment of this invention is to provide a heterogeneouscatalyst composition or system for the dimerization and oligomerizationof higher alpha-olefins in the range of C₅-C₁₂. Such products may beuseful as synthetic lubricant intermediates, particularly for themanufacture of polyalphaolefins (PAO) based on dimerization andoligomerization of C₁₀-C₁₂ alpha-olefins.

A particularly preferred embodiment of the invention is to provide anefficient, heterogeneous catalyst system for the polymerization ofisobutylene to produce highly reactive polyisobutylene.

Activated metal oxide catalysts of the invention of the presentapplication are prepared by reacting normally liquid BF₃/alcoholcomplexes with anhydrous crystalline aluminum oxide (alumina). Gamma andtheta alumina are the preferred crystalline structures.

BF₃-alumina compositions of the prior art either are not catalytic forsome organic conversion reactions, as reported in U.S. Pat. No.6,710,140. Moreover, in some cases at BF₃ levels that might becatalytic, the BF₃ leaches off and requires additional BF₃ to be addedalong with the reactant feed. This, of course, defeats the purpose of asolid heterogeneous catalyst since post treatment of the reactoreffluent is required to remove the BF₃ residues.

In accordance with the invention of the present application, it has beenunexpectedly found that if normally liquid BF₃/alcohol complexes areused instead of BF₃ gas, the resulting reaction products withcrystalline alumina are highly catalytic, are stable, have a long life,are not deactivated or consumed during the catalytic process. Moreover,high loadings of BF₃ may be achieved without the problem of BF₃ leachinginto the reaction mixture.

Suitable crystalline alumina types include theta alumina and gammaalumina. The more preferred crystal structure is gamma alumina becauseit has a higher capacity for BF₃/alcohol catalyst complexes than doestheta alumina. Alpha alumina is least preferred.

The alumina must be essentially dry before reaction with the BF₃/alcoholcomplex. This may be accomplished by heating the same at 200° C. for10-20 hours.

The BF₃/alcohol complex may be formed by passing BF₃ gas through asolution of pure anhydrous alcohol at a rate that allows the BF₃ to beefficiently absorbed. The ratio of alcohol to BF₃ may generally rangefrom about 0.5 moles of alcohol per mole of BF₃ to about 2 moles ofalcohol per mole of BF₃. A more preferred range is from about 1 mole ofalcohol per mole of BF₃ to about 2 moles of alcohol per mole of BF₃. Themost preferred range is from about 1 mole of alcohol per mole of BF₃ toabout 1.3 moles of alcohol per mole of BF₃.

Alcohols in the range of C₁-C₁₀, with no alpha hydrogens, are suitablefor complexing with BF₃. Alcohols that have alpha hydrogens are easilydehydrated by BF₃ to form olefins. Even if BF₃/alcohol complexes may beformed at low temperatures, for example, the resulting complexes are notstable at reaction temperatures. The more preferred alcohols aremethanol and neo-alcohols, such as neopentyl alcohol. The most preferredalcohol is methanol.

Glycols and polyhydric alcohols with no alpha hydrogens may also beused; for example ethylene glycol.

The reaction of the BF₃/alcohol complex with alumina is highlyexothermic and must be controlled to avoid loss of BF₃. The BF₃/alcoholcomplex may be added by any mechanical means that allows good mixing ofthe complex with the alumina and that also allows for adequatetemperature control. A preferred method is to add the alumina to arotating double cone mixer and meter in the BF₃/alcohol complex suchthat the temperature is controlled within the desired range. Thetemperature during the mixing should not exceed 50-60° C.

The concentration of BF₃/alcohol complex on the alumina may range fromabout 10 to about 30% by weight. A preferred range is from about 20 toabout 30% by weight. The most preferred range is from about 25 to 30% byweight. The actual concentration of F or B in the BF₃/alcoholcomplex-alumina system depends on the alcohol used.

The final catalyst composition (system), which is a BF₃/alcohol-aluminareaction product, may be used to catalyze organic compound conversionreactions. The catalyst composition may be contacted with the reactantsin a batch or a continuous processes.

In a preferred embodiment of the invention, the reactor may be a shellin tube heat exchanger in which the catalyst composition is packed inthe tubes. Such an arrangement may be referred to as a fixed bedreactor. This is especially suitable for highly exothermic reactionssuch as olefin polymerization, particularly isobutylene polymerization.

The exchanger may be situated vertically. The heat exchange media may becirculated through the shell side of the exchanger. The exchanger may beeither a single or multiple pass type. A two pass exchanger isparticularly desirable. The exchanger may be fitted with a recirculationloop to accommodate a volumetric recirculation flow. Theolefin-containing feed stock may enter the reactor via a recirculationpump at a location downstream from the pump. The recirculation pumppushes the olefin stream through the reactor tubes and returns thestream to the suction side of the pump. In the case of the two-pass heatexchanger, the recirculation flow may enter through the bottom of thereactor, then pass through the tubes, exit the reactor from the bottomand return to the pump. This flow scheme constitutes what is generallyconsidered a loop reactor. The pump speed, or an internal recirculationloop on the pump itself, is used to control the flow rate. The flow ratepreferably may be sufficient to generate a velocity that causesturbulent, or at least non-laminar flow of the olefin feed stream overthe fixed bed catalyst composition packed in the tubes.

A volumetric feedstock flow may enter the recirculation loop via a feedpump at a location between the outlet of the recirculation pump and thebottom of the reactor at the beginning of the first pass. Atequilibrium, the concentrations of the olefin monomer and the polymerproducts is constant throughout the reactor so the point at which thereaction effluent leaves the reactor is a matter of choice. However, itmay be convenient for the effluent line to be located at the top of thereactor after the first pass. The effluent flow rate is necessarilyequal to the volumetric feedstock flow rate. The volumetric feedstockflow rate is independent of the volumetric recirculation flow rate anddesirably may be adjusted so as to achieve a desired residence time andconversion.

The reactor may be fitted with appropriate temperature, pressure andflow indicators and controllers necessary to operate under controlledconditions.

The size of the heat exchanger reactor is arbitrary and is based on thedesired volume of product. A convenient size is 10-15 feet in length and4-6 feet in diameter. The number of tubes in the reactor and thediameter of the tubes depend on the catalyst type, size and shape and onthe desired output. A convenient number of tubes, for the above reactorsize, is 150-200 tubes per pass, with an internal diameter of ½ to 1inch. In a two pass exchanger, the tubes extend the full length of thereactor vertically and are connected by end caps at the top and bottomof the reactor. The olefin reaction mixture is directed into one side ofthe bottom end cap and is returned through the other side of the bottomend cap. The interior of the top end cap is open with a outlet for thereaction effluent.

In a preferred embodiment, the reactor pressure may preferably be atleast 150 psig or least at a sufficient level to ensure that a liquidphase is maintained in the reactor. The pressure may be controlled bymeans of a back pressure regulator on the reactor effluent line.

The reactor may desirably be operated at temperatures and conditions toproduce polymer products in the molecular weight range, in the case ofpolyisobutylene, of about 300 to about 5,000 Daltons Other temperaturesand conditions may be used as required for specific organic conversionreactions.

The volumetric recirculation flow rate may be adjusted to provide a heattransfer coefficient of about 40-60 BTU/min-ft²-° F. The volumetricfeedstock flow rate may be maintained at rate to give a Liquid HourSpace Velocity (LHSV) of 1-30 kg isobutylene/kg catalyst. Morepreferably, the LHSV may be controlled at from about 3-10 kgisobutylene/kg catalyst.

A preferred olefin feedstock is C₄ raffinate, also known as raffinate-1or raff-1. The actual composition of such a stream is variable dependingon the source, but a typical raff-1 stream might contain about 0.5 wt %C₃, about 4.5 wt % isobutane, about 16.5 wt % n-butane, about 38.5 wt %1-butene, about 28.3 wt % isobutylene, about 10.2 wt % cis- andtrans-2-butene and less than 0.5 wt % butadiene and less than 1.0 wt %oxygenates. The presence of oxygenates may or may not affect thecatalytic reaction. The C₃s and the n-butane are inert and pass throughthe reactor unchanged and are removed from the reaction mixture in thedownstream stripping steps. The isobutylene reacts to a high degreedepending on the reaction conditions and the desired final product. The1- and 2-butenes may react to varying degrees depending on the catalysttype and reactor conditions. The unreacted olefins are also removed fromthe polymer product in the downstream stripping steps. Raff-1 feedstocks are particularly preferred for production of polymers in whichhigh reactivity is not important. These products are referred to asconventional PIB or PB.

Another preferred olefin feedstock is the effluent from thedehydrogenation of isobutane to isobutylene, referred to simply asdehydro effluent, or DHE. DHE typically contains about 42-45 wt %isobutene, and about 50-52 wt % isobutane with the balance being smallamounts of C₃, normal butanes and butylenes, and butadiene. Thisfeedstock is particularly suitable for production of polyisobutylene inlocations in which the inert isobutane may be utilized, for example incooperation with an isobutane dehydrogenation unit.

Another preferred olefin feedstock is DHE in which most of the inertisobutane has already been removed. This stream is known as IsobutyleneConcentrate and typically contains about 88-90 wt % isobutene, and about5-10 wt % isobutane, with the balance being minor amounts of C₃, normalbutanes and butylenes, and butadiene. This feedstock is also suitablefor production of highly reactive polyisobutylene.

Yet another preferred olefin feedstock is high purity isobutylene whichcontains greater than 99 wt % isobutylene. This feedstock is highlysuitable for the production of highly reactive polyisobutylene.Unreacted olefin may be easily recycled.

After leaving the reactor, the reaction effluent may be purified simplyby atmospheric and/or vacuum stripping to remove light byproducts andinerts. The unreacted monomers maybe be recycled, but provisions must bemade to separate or purge the inerts depending on the olefin feed type.

Because the reaction scheme discussed above allows for a very efficientremoval of the heat of reaction such that isothermal and CSTR(Continuous Stirred Tank Reactor) conditions may be maintained, thevolumetric efficiency is very high. That is, a large volume of productmay be produced for a given reactor volume. Therefore the capital costper volume of product is very low. The fact that downstream catalystremoval and/or catalyst regeneration equipment is not required furtherimpacts the total capital cost in a positive manner.

Table I below shows a comparison between prior and current commercialprocesses for making polyisobutylene and the process of the invention ofthe present application employing the novel BF₃/alcohol-metal oxidecatalyst system of the invention. In the Table 1, the column labeled“Soltex” refers to the invention of the present application. Inaddition, the term IB refers to isobutylene.

TABLE 1 COMPARISON OF PIB PROCESS TERMINOLOGY Component ConventionalBASF/Oronite TPC Soltex Reactor Large, high Large, high Low volume Lowvolume fixed volume, fluidized volume CSTR, tubular loop bed loopreactor, bed, 2,000-4,000 gal 2,000-4,000 gal reactor, 30-50 gal 50-100gal LHSV 1-2 1-2 5-10 5-10 (bed wt per hr) Catalyst Solid AlCl3 slurryBF3 gas mixed in- Premixed BF3- Solid catalyst situ with modifier,methanol co-fed packed in tubes of Premixed catalyst with feed. Controlreactor. No need not stable issues. Catalyst is to co-feed with IB.stable, no BF3 Simplifies gas operating scheme Feed Raff-1 High purityIB IB concentrate, High purity IB, no diluted with 80-90% dilutionhexane Cat Removal Filtration/water Quench w/base Quench None wash.followed by series w/NH4OH, Neutralization of of water washes followedby two Al salts mixer/settler water washes. Requires Neutralization ofNH4OH Waste Al salts BF3 aqueous salts BF3 aqueous salts None HighReactive No Yes Yes Yes C4 removal C4 flasher at 50-90 C4 flasher at50-90 C4 flasher at 50-90 C4 flasher at 50-90 psig psig psig psig LightPolymer Atm stripper, Atm stripper, Atm stripper, Atm stripper, Removalvacuum distillation vacuum distillation vacuum distillation vacuumdistillation

The above description of an isobutylene polymerization process has beenused to illustrate the utility of the activated metal oxide catalystsystem of the invention of the present application. Such description ofa preferred embodiment was not meant to limit the scope of theinvention. The BF₃/alcohol-metal oxide reaction product of the inventionmay be used as a catalyst in connection with any organic productreaction that requires an acid catalyst. These reactions include, butare not limited to, Friedel-Crafts alkylation, phenolic alkylation,isoparaffin alkylation, olefin dimerization and polymerization ingeneral, higher alpha olefin dimerization and isobutylene dimerizationamong others.

The foregoing disclosure and description of the invention isillustrative and explanatory thereof. Various changes in the details ofthe described method may be made without departing from the true spiritof the invention.

1. A catalyst system for heterogeneous catalysis of an organic compoundconversion reaction, said system comprising a reaction product of (i) aBF₃/alcohol catalyst complex and (ii) an activated metal oxide supportfor said catalyst complex, said reaction product including an amount ofsaid catalyst complex effective for catalyzing said conversion reaction.2. A catalyst system as set forth in claim 1, wherein said conversionreaction comprises Friedel-Crafts alkylation, phenolic alkylation,olefin dimerization, olefin oligomerization, olefin polymerization,propylene oligomerization, propylene polymerization, butylenedimerization, butylene oligomerization, isobutylene dimerization,isobutylene oligomerization, butylene polymerization, isobutylenepolymerization or isoparaffin alkylation.
 3. A catalyst system as setforth in claim 1, wherein said alcohol has no alpha hydrogen.
 4. Acatalyst system as set forth in claim 3, wherein said alcohol comprisesa C₁-C₁₀ monohydric alcohol, glycol or polyhydric alcohol.
 5. A catalystsystem as set forth in claim 1, wherein said alcohol is methanol.
 6. Acatalyst system as set forth in claim 5, wherein the concentration ofsaid catalyst complex on the alumina ranges from about 10 to about 30%by weight.
 7. A catalyst system as set forth in claim 6, wherein theconcentration of said catalyst complex on the alumina ranges from about25 to about 30% by weight.
 8. A catalyst system as set forth in claim 1,wherein said system is in the form of a fixed bed.
 9. A catalyst systemas set forth in claim 1, wherein said conversion reaction comprisespolymerization of isobutylene to form a polyisobutylene product.
 10. Acatalyst system as set forth in claim 1, wherein said activated metaloxide support comprises gamma alumina.
 11. A catalyst system as setforth in claim 5, wherein the ratio of alcohol to BF₃ in said catalystcomplex ranges from about 0.5 mole of alcohol per mole of BF₃ to about 2moles of alcohol per mole of BF₃.
 12. A catalyst system as set forth inclaim 11, wherein the ratio of alcohol to BF₃ in said catalyst complexranges from about 1 mole of alcohol per mole of BF₃ to about 1.3 molesof alcohol per mole of BF₃.
 13. A catalyst system for heterogeneouscatalysis of an isobutylene polymerization reaction, said systemcomprising a reaction product of (i) a BF₃/methanol catalyst complex and(ii) a gamma alumina support for said catalyst complex, wherein theratio of alcohol to BF₃ in said catalyst complex ranges from about 0.5mole of alcohol per mole of BF₃ to about 2 moles of alcohol per mole ofBF₃, wherein the concentration of said catalyst complex on the aluminaranges from about 10 to about 30% by weight.
 14. A catalyst system asset forth in claim 13, wherein said system is in the form of a fixedbed.
 15. A method for preparing a catalyst system for heterogeneouscatalysis of an organic compound conversion reaction, said methodcomprising reacting (i) a BF₃/alcohol catalyst complex and (ii) anactivated metal oxide support for said catalyst complex, wherein saidreaction product includes an amount of said catalyst complex effectivefor catalyzing said conversion reaction.
 16. A method as set forth inclaim 15, wherein said alcohol has no alpha hydrogen.
 17. A method asset forth in claim 16, wherein said alcohol is methanol.
 18. A method asset forth in claim 15, wherein the concentration of said catalystcomplex on the alumina ranges from about 10 to about 30% by weight. 19.A method as set forth in claim 15, wherein said conversion reactioncomprises polymerization of isobutylene to form a polyisobutyleneproduct.
 20. A method as set forth in claim 15, wherein said activatedmetal oxide support comprises gamma alumina.
 21. A method as set forthin claim 15, wherein the ratio of alcohol to BF₃ in said catalystcomplex ranges from about 0.5 mole of alcohol per mole of BF₃ to about 2moles of alcohol per mole of BF₃.
 22. A method for preparing a catalystsystem for heterogeneous catalysis of an isobutylene polymerizationreaction, said method comprising reacting (i) a BF₃/methanol catalystcomplex and (ii) a gamma alumina support for said catalyst complex,wherein the ratio of alcohol to BF₃ in said catalyst complex ranges fromabout 0.5 mole of alcohol per mole of BF₃ to about 2 moles of alcoholper mole of BF₃, wherein the concentration of said catalyst complex onthe alumina ranges from about 10 to about 30% by weight.
 23. A methodfor conducting an organic compound conversion reaction comprisingcontacting a selected reactive organic compound with a catalyst systemas set forth in claim
 1. 24. A method as set forth in claim 23, whereinsaid system is in the form of a fixed bed.
 25. A method for conductingan isobutylene polymerization reaction comprising contacting isobutylenewith a catalyst system as set forth in claim
 13. 26. A method as setforth in claim 25, wherein said system is in the form of a fixed bed.